Characterization of microstructure of Nano-TiO2 coating deposited by vacuum cold spraying

Control of the microstructure of TiO₂ coatings through preparation methods significantly influences the coating performance. In this study, a vacuum cold-spray process, as a new coating technology, is used to deposit nanocrystalline TiO₂ coatings on conducting glass and stainless steel substrates. TiO₂ deposits were formed using two types of nanocrystalline TiO₂ powders with mean particle diameters of 200 and 25 nm. Coating microstructures were characterized by scanning electron microscopy and x-ray diffraction analysis. Results demonstrate that a thick nanocrystalline TiO₂ coating can be deposited by the vacuum cold-spray process. The coating was found to consist of particles stacked as agglomerates that build up to several hundred nanometers. The coating also presents a mesoporous microstructure that could be effective in such applications as photocatalytic degradation and dye-sensitized solar cells. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Influence of Annealing on Photocatalytic Performance and Adhesion of Vacuum Cold-Sprayed Nanostructured TiO2 Coating

Composite powder was prepared using primary nanoTiO₂ powder and polyethylene glycol (PEG). The nanoTiO₂ coating was deposited through vacuum cold spray using both the composite powder and the primary nanopowder. The influence of annealing on the coating adhesion and photocatalytic activity was investigated. The coating adhesion was evaluated through erosion test by water jet. The photocatalytic performance of the coatings was evaluated through photodegradation of phenol in water. Results showed that annealing of the coating at a temperature from 450 to 500 °C yielded both higher activity and better adhesion. The adhesion of the coating deposited using the composite powder was better than that using the primary nanoTiO₂ powder. It was found that the TiO₂ coating, resulting from the composite powder, presented much higher activity than that deposited with the primary nanopowder. The better activity is attributed to the existence of large pores resulting from the stacking of composite powder, which benefits the reactants’ transportation through the porous coating. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.     

Strategy to Improve the Performance of Dye-sensitized Solar Cells Based on TiO2 Films Prepared by Room Temperature Cold Spray

Dye-sensitized solar cells(DSCs)are promising photochemical solar cells owing to their high efficiency and low cost.In this study,the influence of cell geometry,electrolyte composition,and counter electrode(CE)characteristics on the performance of DSCs was investigated to aim at improving the cell efficiency.Using an U-type cell geometry proposed decreased the internal resistance of DSCs and therefore increased the fill factor and energy conversion efficiency.The addition of DMPII to the I-/I3-based electrolyte increased the open-circuit voltage by decreasing the dark current.Compared to the DSCs with the Pt CE prepared by the thermal decomposition of H2PtCl6,the DSCs with the sputtered Pt CE showed a higher fill factor and short-circuit current density,owing to the high electrical conductivity and enhanced light-reflecting ability of the mirror-like sputtered Pt CE.Based on these results,the energy conversion efficiency of the DSC with the TiO2 porous films fabricated by a room temperature cold spray method was increased from 3.93%to 5.11%.The relatively high efficiency shows that the room temperature cold spray is a prospective method in fabricating nanocrystalline TiO2 films for flexible DSCs.     

Characterization of Nanostructured WC-Co Deposited by Cold Spraying

Nanostructured WC-Co coating was deposited by cold spraying using a nanostructured WC-12Co powder. The critical velocity for the particle to deposit was measured. The coating microstructure was characterized by X-ray diffraction analysis, scanning electron microscopy, and transmission electron microscopy. The coating hardness was tested using a Vickers hardness tester. The deposition behavior of single WC-Co particle was examined. WC particle size was measured for comparison of deposit properties to that of sintered bulk. The result shows that the nanostructured WC-Co coating can be successfully deposited by cold spraying using nanostructured powders. The coating exhibited a dense microstructure with full retention of the original nanostructure in the powder to the coating. The test of microhardness of the coating yielded a value of over 1820 Hv_0.3, which is comparable to that of sintered nanostructured WC-Co. The deposition behavior of WC-Co powders as superhard cermet materials in cold spraying and powder structure effects is discussed. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.     

Influence of Silver Doping on Photocatalytic Activity of Liquid-Flame-Sprayed-Nanostructured TiO2 Coating

Silver ion was added to liquid feedstock to deposit Ag⁺-doped-nanostructured TiO₂ photocatalytic coatings through liquid-flame spraying. The coating microstructure was characterized by x-ray diffraction (XRD). The photocatalytic performance of coatings was examined by photodegradation of acetaldehyde. The XRD analysis showed that the phase structure of coatings was not significantly influenced by the silver ion doping. However, a shift was found for XRD peaks of anatase TiO₂. The photocatalytic activity of the TiO₂ coatings increased and then decreased with the increase of dopant concentration. The photocatalytic activity of doped coatings was higher than that of pure TiO₂ coating, regardless of the dopant concentration. The enhancement of photocatalytic performance of doped coatings is attributed to co-doping of Ag⁺ ion and metallic Ag. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.     

TiO2/膨润土复合光催化材料的常温制备及性能研究

采用改进的溶胶-凝胶法,在以水为主要溶剂的反应体系中,控制钛酸四丁酯充分水解、缓慢聚合,在 常压、低温(70℃)的温和条件下制备出稳定的TiO₂纳米晶溶胶,并利用TiO₂纳米晶溶胶在膨润土表面负载,获得TiO₂/膨润土复合光催化材料。采用 X 射线衍射、扫描电镜、比表面积测定等研究手段对样品的结构形貌进行了表征,并考察了其光催化活性。结果表明：较高的水用量有利于TiO₂晶体形成,当去离子水:钛酸四丁酯摩尔比大于167:1时,在溶胶体系中出现了锐钛矿型TiO₂纳米晶体;TiO₂纳米晶主要负载于膨润土表面,并未嵌入到膨润土层间结构,但相对于单一膨润土,TiO₂负载显著提高了材料比表面积;当去离子水:钛酸四丁酯摩尔比=192:1时,在紫外光照射下,复合光催化材料表现出最高的光催化活性,对亚甲基蓝的降解率达到93.8%。     

Influence of pore structure on ion diffusion property in porous TiO2 coating and photovoltaic performance of dye-sensitized solar cells

The ion diffusion in porous TiO₂ coating determines the limiting current density and the photovoltaic performance of a dye-sensitized solar cell. Nano-TiO₂ coatings with unimodal nano-size distribution and bimodal size distribution were deposited by vacuum cold spray to examine the effects of the pore structure on the ion diffusion property and cell performance. Results show that the I₃⁻ ion diffusion coefficient increased with the increase in the mean pore size. The bimodal size distribution of nanometer-sized and submicrometer-sized pores in the coating was found to have a synergistic enhancement effect on the ion diffusion. Better ion diffusion performance contributed to a higher open circuit voltage. The optimal coating thickness (~ 30 μm) was nearly doubled in the cells with bimodal pore size distribution, compared with the previously reported optimal coating thickness (~ 15 μm) in the cell with unimodal pore size distribution. The reason is attributed to the high ion diffusion coefficient which allows a high limiting current density.     

Effect of Cu2+ doping on photocatalytic performance of liquid flame sprayed TiO2 coatings

Cu²⁺ was added to liquid feedstock to deposit ion doping TiO₂ photocatalytic coatings through liquid flame spraying. The coating microstructure was characterized by x-ray diffraction (XRD), transmission electron microscopy, and x-ray photoelectron spectroscopy (XPS). The photocatalytic performance of coatings was examined by photodegradation of acetaldehyde. The XRD analysis shows that the crystalline structure of coatings is not significantly influenced by Cu²⁺ doping. The photocatalytic activity of the TiO₂ coatings is enhanced by Cu²⁺ doping. It is found that a high concentration of Cu²⁺ doping decreases the activity. The XPS analysis shows that the adsorbed oxygen concentration is increased with the increase of Cu²⁺ dopant concentration and decreases with a further increase of dopant concentration. The enhancement of photocatalytic activity can be attributed to the adsorption ability of oxygen and other reactants on the surface of doping TiO₂ coatings. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Influence of TiCl4 treatment on performance of dye-sensitized solar cell assembled with nano-TiO2 coating deposited by vacuum cold spraying

Titanium tetrachloride (TiCl4) treatment was employed to TiO2 coating deposited on fluoride-doped tin oxide (FTO) conducting glass and indium oxide doped tin oxide (ITO) conducting glass, respectively. The nano-crystalline TiO2coating was deposited using a composite powder composed of polyethylene glycol (PEG) and 25 nm TiO2 particles by vacuum cold spraying (VCS) process. A commercial N-719 dye was used to adsorb on the surface of TiO2 coating to prepare TiO2 electrode, which was applied to assemble dye-sensitized solar cell (DSC).The cell performance was measured under simulated solar light at an intensity of 100 mW·cm-2.Results show that with an FTO substrate the DSC composed of a VCS TiO2 electrode untreated by TiCl4 gives a short-circuit current density of 13.1 mA·cm-2 and an open circuit voltage of 0.60 V corresponding to an overall conversion efficiency of 4.4%. It is found that after TiCl4 treatment to the VCSTiO2 electrode with an FTO substrate, the short circuit current density of the cell increases by 31%, the open-circuit voltage increases by 60 mV and a higher conversion yield of 6.5% was obtained. However, when an ITOsubstrate is used to deposit TiO2 coating by VCS, after TiCl4 treatment, the conversion efficiency of the assembled cell reduces slightly due to corrosionof the conducting layer on the ITO glass by TiCl4.     

团聚粉末制备工艺对冷喷涂Ti2AlC沉积的影响

以热压烧结后球磨粉碎的Ti_2AlC亚微米粉末为原料,通过水热处理使其团聚成微米级粉末,并运用冷喷涂技术在Zr-4合金基体上沉积Ti_2AlC涂层。采用扫描电子显微镜、金相显微镜、XRD衍射仪、激光粒度分析仪等对Ti_2AlC颗粒和涂层微观结构进行表征;采用显微硬度仪和拉伸测试系统对Ti_2AlC涂层的基本力学性能进行测试;采用N2吸附法测涂层孔隙,采用电化学工作站测涂层的贯通孔隙。结果表明:对平均粒径0.3μm的Ti_2AlC粉末进行水热处理时,添加硫酸铵能够促进亚微米颗粒的团聚,团聚粉末的平均粒度可达到6μm。此粉末的冷喷涂特性最好,沉积的Ti_2AlC涂层厚度达到100μm,涂层中有微孔和介孔但没有贯通孔隙,涂层和基体结合强度达到了44MPa。     

La2O3改性ZrB2-SiC涂层C/C复合材料全温域抗氧化行为研究

采用高温反应熔渗工艺制备了ZrB2-SiC和La2O3改性ZrB2-SiC涂层C/C复合材料,对比了2种涂层试样在中温(7001100℃)、高温(12001500℃)和超高温(2000℃以上)3个温域范围内的抗氧化性能。结果表明:7001100℃范围内,随着温度的升高,La2O3改性涂层试样的抗氧化性能提升幅度在逐渐提高。1200℃1500℃范围内,涂层均表现出良好的长时抗氧化性能,La2O3改性ZrB2-SiC在1200℃下恒温氧化250 h后,仍保持微量的增重;涂层复合材料良好的高温抗氧化性能主要其在是由于氧化过程中涂层表面形成的La-Si-O复合玻璃层和钉扎相ZrSiO4的协同作用提升了氧化膜的高温稳定性。在2000℃以上的氧乙炔火焰烧蚀环境下,La2O3的添加使得ZrB2-SiC涂层的质量烧蚀率和线烧蚀率均降低了近50%,其主要归因于表层La-Si-O和ZrO2玻璃层对烧蚀缺陷的愈合作用。     

Deposition of Al2O3-TiO2 Nanostructured Powders by Atmospheric Plasma Spraying

Al₂O₃-13%TiO₂ coatings were deposited on stainless steel substrates from conventional and nanostructured powders using atmospheric plasma spraying (APS). A complete characterization of the feedstock confirmed its nanostructured nature. Coating microstructures and phase compositions were characterized using SEM, TEM, and XRD techniques. The microstructure comprised two clearly differentiated regions. One region, completely fused, consisted mainly of nanometer-sized grains of γ-Al₂O₃ with dissolved Ti⁺⁴. The other region, partly fused, retained the microstructure of the starting powder and was principally made up of submicrometer-sized grains of α-Al₂O₃, as confirmed by TEM. Coating microhardness as well as tribological behavior were determined. Vickers microhardness values of conventional coatings were in average slightly lower than the values for nanostructured coating. The wear resistance of conventional coatings was shown to be lower than that of nanostructured coatings as a consequence of Ti segregation. A correlation between the final properties, the coating microstructure, and the feedstock characteristics is given.     

AgSnO2触点涂层的组织与性能

采用高能球磨方法制备Ag-SnO₂复合粉末,将球磨粉末冷喷涂到铜基板上,能够获得几毫米厚度的较致密的AgSnO₂触点涂层。850 ℃退火后涂层发生进一步致密化并且在原始粉末颗粒边界形成富银区,涂层材料硬度略为降低。电弧侵蚀和电接触试验表明,冷喷涂的AgSnO₂涂层材料具有低而稳定的接触电阻,能够满足触点的基本性能要求。     

Modification of TiO2 nanorods by Bi2MoO6 nanoparticles for high performance visible-light photocatalysis

In this work, TiO₂ nanorods were prepared by a hydrothermal process and then Bi₂MoO₆ nanoparticles were deposited onto the TiO₂ nanorods by a solvothermal process. The nanostructured Bi₂MoO₆/TiO₂ composites were extensively characterized by X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy. The photocatalytic activity of the Bi₂MoO₆/TiO₂ composites was evaluated by degradation of methylene blue. The Bi₂MoO₆/TiO₂ composites exhibit higher catalytic activity than pure Bi₂MoO₆ and TiO₂ for degradation of methylene blue under visible light irradiation (λ > 420 nm). Further investigation revealed that the ratio of Bi₂MoO₆ to TiO₂ in the composites greatly influenced their photocatalytic activity. The experimental results indicated that the composite with Bi₂MoO₆:TiO₂ = 1:3 exhibited the highest photocatalytic activity. The enhancement mechanism of the composite catalysts was also discussed.     

纳米颗粒增强TiO_2涂层的制备及其防污性能

为提高二氧化钛涂层的防污性能,采用KH-550硅烷改性锐钛矿型TiO_2颗粒,并充分分散于二氧化钛凝胶涂层中。通过降解亚甲基蓝溶液、细菌贴附试验、藻类贴附试验,分别评价了涂层的光催化性能、抗菌性能及抗藻类附着性能,并利用激光共聚焦显微镜及扫描电子显微镜对藻类在涂层表面的附着情况进行分析。结果表明,添加TiO_2纳米颗粒涂层的防污性能较未添加TiO_2纳米颗粒涂层有较大程度的提高。添加粒径为5~10 nm TiO_2颗粒的二氧化钛涂层对小球藻、三角褐指藻及小新月菱形藻的附着降低率分别达到了92.1%、71.5%和62.1%,相较于纯二氧化钛涂层对3种藻类的附着降低率分别提高了29.7%、68.4%和43.5%。TiO_2颗粒的加入可以有效地提高涂层的光催化性能,光催化使得涂层具有亲水、抗菌及自清洁的性能进而有利于提高涂层的防污性能。     

Preparation of TiO<Subscript>2</Subscript> Nanopowders by Plasma Spray and Characterizations

TiO₂ powders with the range of 10-60 nm were prepared successfully by plasma spray in the self-developed plasma spray equipment. The prepared nanopowders were characterized by transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The results showed that the prepared TiO₂ nanopowders were the mixture of anatase phase and rutile phase, the main phase was anatase. There were O, Ti, and C elements in powders; Ti element still existed in tetravalent. The photocatalytic degradation of methyl orange indicated that all methyl orange (20 mg/L) can be degraded fully when the addition of prepared TiO₂ nanopowders and illumination time were 1 g/L and 150 min, respectively.     

超音速等离子喷涂NiCrCr3C2/Mo复合涂层的高温摩擦磨损性能*

采用超音速等离子喷涂制备了NiCr-Cr3C2/Mo复合涂层,借助扫描电子显微镜(SEM)、能谱仪(EDS)、显微硬度计、高温摩擦磨损试验机等手段,研究了涂层的微观组织、显微硬度及涂层在25、300、500、750℃下的摩擦磨损性能。结果表明:制备的NiCr-Cr3C2/Mo复合涂层Mo相分布均匀,组织致密、硬度高;温度对涂层的摩擦因数影响显著,随温度的升高,摩擦因数呈先下降后上升再下降的趋势,750℃时因摩擦界面生成MoO3减摩相使摩擦因数最低;NiCr-Cr3C2/Mo复合涂层在高温下以氧化疲劳剥落为主要失效机制,涂层表面复合氧化膜的形成特点将直接影响涂层的摩擦磨损性能,MoO3的形成是显著提高涂层减摩效果的主要因素。     

基于磁过滤技术的热障涂层表面Al2O3 覆盖层抗CMAS腐蚀性能

为了提高热障涂层（TBC）的抗沉积物（主要成分为CaO、MgO、Al₂O₃和SiO₂,简称CMAS）腐蚀性能,采用磁过滤阴极真空电弧（FCVA）技术在TBC表面上制备了致密的Al₂O₃覆盖层,比较和分析了Al₂O₃改性TBC和沉积态TBC的润湿行为和抗CMAS腐蚀性能。结果表明：使用FCVA技术制备Al₂O₃覆盖层的过程对7%（质量分数）氧化钇稳定的氧化锆（7YSZ）相的结构无明显影响,且经Al₂O₃改性的TBC综合性能均优于沉积态TBC。在1250 ℃、CMAS腐蚀条件下,Al₂O₃覆盖层有效地限制了熔融CMAS在TBC表面上的扩散行为。同时,Al₂O₃填充了7YSZ柱状晶之间的间隔并且阻碍了熔融CMAS的渗透,证明了FCVA可作为一种制备Al₂O₃涂层的新方法以提高TBC的抗CMAS腐蚀性能,且Al₂O₃涂层及其制备过程对TBC的热震性能均无消极影响。     

等离子喷涂制备ZrB_2-SiC涂层及其抗氧-丙烷焰流烧蚀性能

为提高C/C复合材料的抗高温烧蚀性能,利用大气等离子喷涂技术在C/C复合材料表面制备ZrB_2-SiC复合涂层,并对其进行抗高温氧-丙烷焰流烧蚀试验。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)及能谱分析仪(EDS)对涂层的物相成分、微观形貌等进行检测分析。结果表明:大气等离子喷涂能在C/C复合材料表面制备出均匀致密的ZrB_2-SiC复合涂层,涂覆有ZrB_2-SiC涂层的C/C复合材料分别承受1 600、1 700和1 800℃的氧-丙烷焰流烧蚀300 s后依次增重0.63%、0.76%和0.71%,而烧蚀600s后试样质量烧蚀率分别为9.42×10~(-5)、2.04×10~(-4)和1.04×10~(-3)g/s。ZrB_2-SiC涂层显著提高了C/C复合材料的抗烧蚀性能,涂层氧化生成的玻璃态SiO_2能有效填充孔隙。直到SiO_2耗尽,涂层烧蚀后的孔洞成为环境中的氧进入基体的通道,导致基体烧蚀。     

Plasma spray coating of spray-dried Cr2O3/wt.% TiO2 powder

An agglomerated Cr₂O₃/wt.%TiO₂ powder has been fabricated by the spray drying process under different parameters. The spray-dried powder has well-agglomerated particles of spherical shape. In the conditions of the high slurry feed rate and low binder concentration in the slurry, the powder has large cavities inside some particles and ruggedness over their surface. The optimum plasma spray feed rate has been found by examining the spraying behavior of the powder and melted state of particles. The plasma spray coating has been performed under different process variables such as spraying distance and plasma power. These parameters strongly affect the characteristics of the coated layer: microstructure, hardness, and bond strength.